KR20090040896A - Aromatic amine derivative and organic electroluminescent device employing the same - Google Patents

Abstract

A novel aromatic amine derivative having a specific structure; and an organic electroluminescent device comprising a cathode, an anode, and one or more organic thin layers sandwiched between the electrodes and comprising a luminescent layer, wherein the organic thin layers include at least one layer, especially a hole-transporting layer, which comprises the aromatic amine derivative alone or contains the derivative as a component of a mixture. Use of the organic electroluminescent device is effective in attaining a reduction in operating voltage. The molecules are less apt to crystallize, and the aromatic amine derivative enables the organic electroluminescent device to be produced in an improved yield and have a long life.

Description

Aromatic Amine Derivatives and Organic Electroluminescent Devices Using Them {AROMATIC AMINE DERIVATIVE AND ORGANIC ELECTROLUMINESCENT DEVICE EMPLOYING THE SAME}

The present invention relates to an aromatic amine derivative and an organic electroluminescent (EL) device using the same. In particular, by using an aromatic amine derivative having a specific substituent as a hole transporting material, the driving voltage is reduced and the crystallization of molecules is suppressed. The present invention relates to an aromatic amine derivative which improves the yield when manufacturing an organic EL device and improves the lifetime of the organic EL device.

An organic EL element is a self-luminous element using the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. Organics have been reported by Eastman Kodak's CWTang et al. For low voltage driving organic EL devices using stacked devices (CWTang, SAVanslyke, Applied Physics Letters, 51, 913, 1987, etc.) There is an active research on organic EL devices having materials as constituent materials. Tang et al. Use tris (8-quinolinolato) aluminum for the light emitting layer and triphenyldiamine derivatives for the hole transport layer. Advantages of the laminated structure include improving the efficiency of injecting holes into the light emitting layer, blocking the electrons injected from the cathode to increase the generation efficiency of excitons generated by recombination, confining excitons generated in the light emitting layer, and the like. Can be mentioned. As in this example, as the device structure of the organic EL element, a two-layer type of a hole transport (injection) layer, an electron transport light emitting layer, or a three-layer type of a hole transport (injection) layer, a light emitting layer, an electron transport (injection) layer and the like are well known. . In such a stacked structure device, a device structure and a formation method have been researched to increase recombination efficiency of injected holes and electrons.

In general, when the organic EL element is driven or stored in a high temperature environment, adverse effects such as a change in the emission color, a decrease in the emission efficiency, an increase in the driving voltage, and a shortening of the emission lifetime are caused. In order to prevent this, it was necessary to raise the glass transition temperature (Tg) of a hole transport material. Therefore, it is necessary to have many aromatic groups in the molecule | numerator of a hole transport material (for example, the aromatic diamine derivative of patent document 1, the aromatic condensed ring diamine derivative of patent document 2), and the structure which has 8-12 benzene rings normally It is preferably used.

However, when there are many aromatic groups in the molecule, crystallization easily occurs when a thin film is formed using these hole transport materials to produce an organic EL device, and the defect of the thin film due to crystallization is prevented due to the outlet of the container used for deposition. Thus, problems such as causing a decrease in yield of the organic EL device have arisen. In addition, a compound having a large number of aromatic groups in a molecule generally has a high glass transition temperature (Tg), but has a low sublimation temperature, and thus has a short lifetime because it is thought that decomposition during deposition or uneven deposition occurs. There was a problem.

On the other hand, there are known documents in which asymmetric aromatic amine derivatives are disclosed. For example, although Patent Document 3 describes an aromatic amine derivative having an asymmetrical structure, there are no specific examples and none of the features of the asymmetric compound are described. In addition, although patent document 4 describes the asymmetric aromatic amine derivative which has phenanthrene as an Example, it handles the same example as a symmetric compound, and does not describe the characteristic of an asymmetric compound at all. In addition, although asymmetric compounds require a special synthesis method, these patents do not specify a description of a method for preparing an asymmetric compound. In addition, although patent document 5 describes the manufacturing method of the aromatic amine derivative which has an asymmetric structure, it does not describe the characteristic of an asymmetric compound. Although patent document 6 has description of the asymmetric compound which has a high glass transition temperature and is thermally stable, only a compound which has carbazole has an illustration.

Moreover, although there exists patent document 7 as a compound which has a furan, only the compound which furan couple | bonded with the amine directly is described. Moreover, although patent documents 7-9 have description of the compound which furan couple | bonded with nitrogen through the aryl group, sufficient performance was not acquired. Therefore, the development of the organic electroluminescent element which has the more excellent performance was strongly desired.

Patent Document 1: US Patent No. 4,720,432

Patent Document 2: US Patent No. 5,061,569

Patent Document 3: Japanese Patent Application Laid-Open No. 8-48656

Patent Document 4: Japanese Patent Application Laid-Open No. 8-135261

Patent Document 5: Japanese Patent Application Laid-Open No. 2003-171366

Patent Document 6: US Patent No. 6,242,115

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-319273

Patent Document 8: Japanese Patent Application Laid-Open No. 19-210-125468

Patent Document 9: Japanese Patent Application Laid-Open No. 19-24-224572

(Initiation of invention)

(Tasks to be solved by the invention)

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is possible to reduce the driving voltage, to hardly crystallize molecules, to improve the yield when manufacturing an organic EL device, and to have a long lifetime, and an organic EL device and an aromatic to realize the same. It is an object to provide an amine derivative.

(Means to solve the task)

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, the present inventors earnestly researched and, when using the novel aromatic amine derivative which has a specific substituent represented by following formula (1) as an organic EL element material, especially a hole transport material, the said subject Found to solve the problem, came to complete the present invention.

Furthermore, it was found that an amino group substituted with an aryl group having a benzothiophene structure represented by the formula (2) or (3) is suitable as the amine unit having a specific substituent. Since the amine unit has a polar group and can interact with the electrode, it is easy to inject charges, and because it has a thiophene structure, the mobility is high and the driving voltage is lowered. Due to the obstacles, the interaction between molecules is small, crystallization is suppressed, the yield of manufacturing organic EL devices is improved, and the lifespan of the organic EL devices obtained is long. It was found that the effect of lowering voltage and long life was obtained. In addition, in a compound having a large molecular weight, a compound having an asymmetric structure can lower the deposition temperature, thereby suppressing decomposition during deposition and extending the life.

That is, the present invention is to provide an aromatic amine derivative represented by the formula (1).

[In Formula 1, L ₁ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

At least one of Ar ₁ to Ar ₄ is represented by the following formula (2).

{In Formula 2, R ₁ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 50 carbon atoms A group, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted Substituted alkoxycarbonyl group, halogen atom, cyano group, nitro group, hydroxy group or carboxyl group.

a is an integer of 0-3.

L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.}

In Chemical Formula 1, each of Ar ₁ to Ar ₄ that is not Chemical Formula 2 is an independently substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, except that the substituents of Ar ₁ to Ar ₄ are substituted or unsubstituted. An aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or An unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a halogen atom, between Anano group, nitro group, hydroxyl group or carboxyl group.]

In addition, the present invention is to provide an aromatic amine derivative represented by any one of the following formulas (4) to (6).

[In Formulas 4 to 6, L ₅ to L ₁₂ represent a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

At least one of Ar ₅ to Ar ₉ is represented by the following formula (7).

At least one of Ar ₁₀ to Ar ₁₅ is represented by the following formula (7).

At least one of Ar ₁₆ to Ar ₂₁ is represented by the following formula (7).

{In Formula 7, R ₁ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 50 carbon atoms A group, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted Substituted alkoxycarbonyl group, halogen atom, cyano group, nitro group, hydroxy group, or carboxyl group having 2 to 50 carbon atoms.

a is an integer of 0-3.

L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.}

In Formulas 4 to 6, Ar ₅ to Ar ₂₁ are each independently a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, except that the substituents at Ar ₅ to Ar ₂₁ are substituted or unsubstituted nuclear atoms 6 To 50 aryl groups, substituted or unsubstituted alkyl groups having 1 to 50 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted nuclei Aryloxy group having 5 to 50 atoms, substituted or unsubstituted arylthio group having 5 to 50 atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, halogen atom, cyano group, nitro Group, a hydroxyl group, or a carboxyl group.]

In addition, the present invention is an organic EL device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer alone contains the aromatic amine derivative. Or it provides the organic electroluminescent element containing as a component of a mixture.

(Effects of the Invention)

The aromatic amine derivative of the present invention and the organic EL device using the same reduce the driving voltage, and are difficult to crystallize molecules, and the yield when manufacturing the organic EL device is improved, and the life is long.

(The best mode for carrying out the invention)

The aromatic amine derivative of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1, L ₁ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms. At least one of Ar ₁ to Ar ₄ is represented by the following formula (2).

[Formula 2]

{In Formula 2, R ₁ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 50 carbon atoms A group, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted Substituted alkoxycarbonyl group, halogen atom, cyano group, nitro group, hydroxy group, or carboxyl group having 2 to 50 carbon atoms. a is an integer of 0-3. L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

In Formula 1, those other than Ar ₂ to Ar ₄ are each independently a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, except that the substituents of Ar ₁ to Ar ₄ are substituted or unsubstituted. Substituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted Or an unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a halogen atom, and Ano groups, nitro groups, hydroxyl groups, or carboxyl groups.

The aromatic amine derivative of the present invention is preferably when the formula (2) is represented by the formula (3).

[Formula 3]

In Formula 3, R ₁ is a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

In the aromatic amine derivative of the present invention, Ar ₁ in Formula ₁ is preferably represented by Formula 2.

In the aromatic amine derivative of the present invention, Ar ₁ and Ar ₂ in the formula (1) are preferably each independently represented by the formula (2).

In the aromatic amine derivative of the present invention, Ar ₁ and Ar ₃ in Chemical Formula 1 are preferably each independently represented by Chemical Formula 2.

In the aromatic amine derivative of the present invention, three or more of Ar ₁ to Ar ₄ in the general formula (1) are different from each other, and are preferably asymmetric.

In the aromatic amine derivative of the present invention, three of Ar ₁ to Ar ₄ in the general formula (1) are the same and are preferably asymmetric.

In the aromatic amine derivative of the present invention, Ar ₁ to Ar ₄ in the general formula (1) are preferably each independently a phenyl group, a biphenyl group, a terphenyl group or a fluorenyl group.

Aromatic amine derivatives of the present invention, in formula (I) is L ₁ is preferably at a biphenyl group, a terphenyl group or a fluorenyl group.

In the aromatic amine derivative of the present invention, L ₂ in the general formula (2) is preferably a phenylene group, a biphenylene group, or a fluorenylene group.

In the aromatic amine derivative of the present invention, R ₁ in the general formula (2) is preferably a phenyl group, a naphthyl group or a phenanthrene group.

In the aromatic amine derivative of the present invention, in Formula 1, Ar ₁ to Ar ₄ are each independently a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group, and L ₁ is a biphenylene group, a terphenylene group, or a fluorenylene group. In Formula 2, L ₂ is preferably a phenylene group, a biphenylene group, or a fluorenylene group.

In addition, the present invention is to provide an aromatic amine derivative represented by any one of the following formulas (4) to (6).

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, L ₅ to L ₁₂ represent a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms. At least one of Ar ₅ to Ar ₉ is represented by the following formula (7). At least one of Ar ₁₀ to Ar ₁₅ is represented by the following formula (7). At least one of Ar ₁₆ to Ar ₂₁ is represented by the following formula (7).

[Formula 7]

In Formula 7, R ₁ represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms , Substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted An alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group having 2 to 50 carbon atoms. a is an integer of 0-3. L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

In Formulas 4 to 6, Ar ₅ to Ar ₂₁ are each independently a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, provided that a substituent of Ar ₅ to Ar ₂₁ is substituted or unsubstituted An aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or An unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a halogen atom, a cyano Group, nitro group, hydroxyl group, or carboxyl group.

The aromatic amine derivative of the present invention is preferred if the above formula (7) is represented by the following formula (8).

{In Formula 8, R ₁ is a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.

In the aromatic amine derivative of the present invention, at least one of Ar ₅ to Ar ₉ in Formula 4 is preferably represented by Formula 7.

In the aromatic amine derivative of the present invention, Ar ₅ in Formula 4 is preferably represented by Formula 7.

In the aromatic amine derivative of the present invention, Ar ₆ and Ar ₈ in Formula 4 are preferably each independently represented by Formula 7.

In the aromatic amine derivative of the present invention, at least one of Ar ₁₀ to Ar ₁₅ in Formula 5 is preferably represented by Formula 7.

In the aromatic amine derivative of the present invention, Ar ₁₀ and Ar ₁₅ in Formula 5 may be each independently represented by Formula 7.

In the aromatic amine derivative of the present invention, Ar ₁₁ and Ar ₁₃ in Formula 5 may be each independently represented by Formula 7.

In the aromatic amine derivative of the present invention, at least one of Ar ₁₆ to Ar ₂₁ in Chemical Formula 6 is preferably represented by Chemical Formula 7.

In the aromatic amine derivative of the present invention, Ar ₁₆ , Ar _18, and Ar ₂₀ in Chemical Formula 6 are preferably each independently represented by Chemical Formula 7.

In the aromatic amine derivative of the present invention, Ar ₅ to Ar ₂₁ in Chemical Formulas 4, 5, and 6 are preferably each independently a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group.

The aromatic amine derivative of the present invention is preferably in the formulas (4), (5) and (6), wherein L ₅ to L ₁₂ are each independently a phenylene, biphenylene group, terphenylene group or fluoreneylene group.

In the aromatic amine derivative of the present invention, L ₂ in the general formula (7) is preferably a phenylene group, a biphenylene group, or a fluorenylene group.

In the aromatic amine derivative of the present invention, R ₁ in the general formula (7) is preferably a phenyl group, a naphthyl group or a phenanthrene group.

In the aromatic amine derivative of the present invention, in Formulas 4, 5, 6, and 7, Ar ₅ to Ar ₂₁ are each independently a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group, and L ₅ to L ₁₂ are each independently phenyl. It is preferable that it is a ethylene, a biphenylene group, a terphenylene group, or a fluoreneylene group, and L <_2> is a phenylene group, a biphenylene group, or a fluoreneylene group.

A substituted or unsubstituted aryl group having 6 to 50 nuclear atoms other than that represented by Formula 2 in Ar ₁ to Ar ₄ in Formula 1, and a substituted or unsubstituted nucleus of R ₁ in Formulas 2, 3, 7 and 8 Examples of the substituted or unsubstituted aryl group having 6 to 50 atoms which are an aryl group having 6 to 50 atoms and a substituent having ₁ to Ar ₄ include a phenyl group, 1-naphthyl group, 2-naphthyl group and 1-anthryl group. Group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl- 4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o -Tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-na Group, a 4-methyl-1-anthryl group, 4'-methyl biphenyl group, 4 "-t- butyl-4--p- terphenyl group, fluoran, and the like X group, a fluorene group.

Among these, Preferably they are a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, and a fluorenyl group.

Examples of L _1, Formula 2, 3, 7 and 8 L _2, and general formula 4 to 6, L ₅ to substituted or nuclear atoms of 6 to 50 aryl group unsubstituted of L ₁₂ in the in the formula (1) wherein Examples of the aryl group include divalent groups.

Examples of formula 2, 3, 7, and R _1, and the alkyl group of the formula (1), 4, 5 and 6 Ar ₁ to Ar ₂₁ in the substituent of a substituted or unsubstituted C 1 -C 50 in at 8, for example a methyl group, an ethyl group , Propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group , 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxyethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t -Butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloro Isopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-die Lomoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodo Ethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-diiodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-tri Iodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino- t-butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1 , 3-dicyanoisopropyl group, 2,3-dicyano-t-butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group 2 nitro isobutyl group, 1,2-dynitroethyl group, 1,3-dinitroisopropyl group, 2,3-dinitro-t-butyl group, 1,2,3-trinitropropyl group, cyclopropyl group, cyclo Butyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like.

The substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, R ₁ in Formulas 2 and 7, and Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5, and 6 is a group represented by -0Y, and As an example, the same example as what was demonstrated by the said alkyl group is mentioned.

Examples of the substituted or unsubstituted C6-C50 aralkyl group which is a substituent of R ₁ in Formulas 2 and 7 and Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5, and 6 include benzyl groups and 1-phenylethyl groups. , 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1 -α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group , 2-β-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group , m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o- Iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl and o-hydroxy Sibenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-between Anobenzyl group, o-cyanobenzyl group, 1-hydroxy-2- phenyl isopropyl group, 1-chloro-2- phenyl isopropyl group, etc. are mentioned.

The substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, which is a substituent of R ₁ in Formulas 2 and 7, and Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5, and 6, is represented by -0Y ', and Y Examples of 'include the same as described for the aryl group.

R ₁ in Formulas 2 and 7 and substituted or unsubstituted arylthio groups having 5 to 50 nuclear atoms which are substituents of Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5 and 6 are represented by -SY ' Examples of Y 'include the same as those described above for the aryl group.

The substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms which is a substituent of R ₁ in Formulas 2 and 7 and Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5, and 6 is a group represented by -C00Y, and Y As an example of, the same thing as what was demonstrated by the said alkyl group is mentioned.

Examples of the halogen atom that is a substituent of R ₁ in Formulas 2 and 7 and Ar ₁ to Ar ₂₁ in Formulas 1, 4, 5, and 6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In formulas (2) and (7), a is an integer of 0-3.

Although the specific example of the aromatic amine derivative represented by General formula (1) of this invention is shown below, it is not limited to these exemplary compounds.

It is preferable that the aromatic amine derivative of the present invention is a material for an organic electroluminescent device.

It is preferable that the aromatic amine derivative of the present invention is a hole transport material for an organic electroluminescent device.

In addition, the present invention is an organic EL device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer alone contains the aromatic amine derivative. Or it provides the organic electroluminescent element containing as a component of a mixture.

In the organic EL device of the present invention, the organic thin film layer preferably has a hole transport layer, and the aromatic amine derivative is contained in the hole transport layer.

In the organic EL device of the present invention, it is preferable that the organic thin film layer has a plurality of hole transport layers, and the aromatic amine derivative is contained in a layer not directly in contact with the light emitting layer.

In the organic EL device of the present invention, the organic thin film layer preferably has a hole injection layer, and the aromatic amine derivative is contained in the hole injection layer.

In the organic EL device of the present invention, it is preferable that the aromatic amine derivative be contained in the hole injection layer as a main component.

Examples of the fluorescent dopant include chelate complexes such as amine compounds, aromatic compounds, and tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives, and the like. It is preferable that it is a compound selected according to the luminescent color requested | required, Especially an arylamine compound and an aryldiamine compound are mentioned, Among these, a styrylamine compound, a styryldiamine compound, an aromatic amine compound, and an aromatic diamine compound are mentioned. More preferred. Furthermore, condensed polycyclic aromatic compounds (except amine compounds) are more preferable. These fluorescent dopants may be used alone or in combination.

As such a styrylamine compound and a styryl diamine compound, what is represented by following Chemical formula A is preferable.

(In Formula A, Ar ³ is a group selected from a phenyl group, naphthyl group, biphenyl group, terphenyl group, stilbene group, distyrylaryl group, Ar ⁴ and Ar ⁵ are each an aromatic hydrocarbon having 6 to 20 carbon atoms) And Ar ³ , Ar ⁴ and Ar ⁵ may be substituted, p is an integer of 1 to 4, and p is preferably an integer of 1 to 2. Any one of Ar ³ to Ar ⁵ is styryl Group, more preferably at least one of Ar ⁴ and Ar ⁵ is substituted with a styryl group.)

Here, as an aromatic hydrocarbon group of 6-20 carbon atoms, a phenyl group, naphthyl group, anthranyl group, phenanthryl group, terphenyl group, etc. are mentioned.

As an aromatic amine compound and an aromatic diamine compound, what is represented by following General formula (B) is preferable.

(In the above formula (B), Ar ⁶ to Ar ⁸ are substituted or unsubstituted aryl groups having 5 to 40 carbon atoms. Q is an integer of 1 to 4, and particularly, q is an integer of 1 to 2.

Here, as the aryl group having 5 to 40 nuclear carbon atoms, for example, a phenyl group, naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, coronyl group, biphenyl group, terphenyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothio Ophenyl group, oxadiazolyl group, diphenylanthranyl group, indolyl group, carbazolyl group, pyridyl group, benzoquinolyl group, fluoranthenyl group, acenaphthofluoranthenyl group, stilbene group, peryleneyl group, chrysene Diary, picenyl group, tripenyleneyl group, rubisenyl group, benzoanthracenyl group, phenylanthranyl group, bisanthracenyl group, or an aryl group represented by the following general formulas C and D, and the like, naphthyl group, anthranyl group, cryo A aryl group represented by a senyl group, a pyrenyl group, or general formula (D) is preferable.

(In Formula C, r is an integer of 1 to 3.)

On the other hand, as a preferable substituent substituted by the said aryl group, a C1-C6 alkyl group (ethyl group, a methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, cyclopene) A methyl group, a cyclohexyl group, etc.), an alkoxy group having 1 to 6 carbon atoms (ethoxy group, methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butoxy group, pentoxy group, hexyloxy group Cyclopentoxy group, cyclohexyloxy group, etc.), an aryl group having 5 to 40 carbon atoms, an amino group substituted with an aryl group having 5 to 40 carbon atoms, an ester group having an aryl group having 5 to 40 carbon atoms, and having 1 to 6 carbon atoms Ester group, a cyano group, a nitro group, a halogen atom etc. which have an alkyl group are mentioned.

As condensed polycyclic aromatic compounds (except amine compounds), naphthalene, anthracene, phenanthrene, pyrene, coronene, biphenyl, terphenyl, pyrrole, furan, thiophene, benzothiophene, oxadiazole, indole, carbazole Condensed polycyclic aromatic compounds such as pyridine, benzoquinoline, fluoranthene, benzofluoranthene, acenaphthofluoranthene, stilbene, perylene, chrysene, pisene, triphenylenine, rubicene, benzoanthracene and the like Derivatives are preferred.

In the organic EL device of the present invention, the layer in contact with the anode in the hole injection layer is preferably a layer containing an acceptor material.

It is preferable to use the aromatic amine derivative of this invention especially for the organic electroluminescent element which emits blue light.

EMBODIMENT OF THE INVENTION Hereinafter, the element structure of the organic electroluminescent element of this invention is demonstrated.

(1) Configuration of organic EL device

As a representative element structure of the organic electroluminescent element of this invention,

(1) anode / light emitting layer / cathode

(2) anode / hole injection layer / light emitting layer / cathode

(3) anode / light emitting layer / electron injection layer / cathode

(4) anode / hole injection layer / light emitting layer / electron injection layer / cathode

(5) anode / organic semiconductor layer / light emitting layer / cathode

(6) anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode

(7) anode / organic semiconductor layer / light emitting layer / adhesion improving layer / cathode

(8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

(9) Anode / Acceptor-containing layer / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(10) anode / insulation layer / light emitting layer / insulation layer / cathode

(11) anode / inorganic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode

(12) anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode

(13) Anode / insulation layer / hole injection layer / hole transport layer / light emitting layer / insulation layer / cathode

(14) anode / insulation layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

Etc. can be mentioned.

Usually, although the structure of (8) is used preferably among these, it is not limited to these.

Although the aromatic amine derivative of this invention may be used for any organic thin film layer of an organic electroluminescent element, it can be used for a light emission band or a hole transport band, Preferably it is used for a hole transport band, Especially preferably, a hole injection layer It is hard to crystallize the molecule, and the yield at the time of manufacturing an organic EL element improves.

As an amount to contain the aromatic amine derivative of this invention in an organic thin film layer, 30-100 mol% is preferable.

(2) translucent substrate

The organic EL device of the present invention is produced on a light-transmissive substrate. The translucent substrate here is a substrate which supports an organic EL element, and the board | substrate which the light transmittance of the visible region of 400-700 nm is 50% or more, and is smooth is preferable.

Specifically, a glass plate, a polymer plate, etc. are mentioned. Examples of the glass plate include soda lime glass, barium strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. Moreover, as a polymer board, polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned.

(3) anode

The anode of the organic EL device of the present invention has a function of injecting holes into the hole transporting layer or the light emitting layer, and it is effective to have a work function of 4.5 eV or more. Specific examples of the positive electrode material used in the present invention include indium tin oxide (ITO), tin oxide (NESA), indium zinc oxide (IZO), gold, silver, platinum, copper and the like.

An anode can be produced by forming these electrode materials into a thin film by methods, such as a vapor deposition method and sputtering method.

Thus, when light emission from a light emitting layer is taken out from an anode, it is preferable to make the transmittance | permeability with respect to light emission of an anode larger than 10%. In addition, the sheet resistance of the anode is preferably several hundred? /? The film thickness of the anode depends on the material as well, but is usually selected in the range of 10 nm to 1 mu m, preferably 10 to 200 nm.

(4) light emitting layer

The light emitting layer of organic electroluminescent element has the function of the following (1)-(3) together.

(1) Injection function: The ability to inject holes from the anode or hole injection layer when an electric field is applied, and to inject electrons from the cathode or electron injection layer.

(2) Transport function: The function of moving the injected charges (electrons and holes) by the force of the electric field

(3) Light emitting function: A function of providing a place for recombination of electrons and holes, and connecting them to light emission

However, there may be a difference between the ease of hole injection and the ease of electron injection, and there may be a slight difference in the transport capacity expressed by the mobility of holes and electrons, but it is preferable to use either electric charge.

As a method of forming this light emitting layer, well-known methods, such as a vapor deposition method, a spin coating method, and an LB method, are applicable, for example. It is preferable that especially a light emitting layer is a molecular deposit film. Here, the molecular deposited film is a thin film formed by depositing from a material compound in a gaseous state, or a film formed by solidifying from a material compound in a solution state or a liquid state. Usually, the molecular deposited film is formed of a thin film (molecular stacked film) formed by the LB method. Can be distinguished by the difference between the aggregated structure and the higher order structure and the functional differences resulting therefrom.

In addition, as in the ratio disclosed in Japanese Patent Application Laid-Open No. 57-51781, a light emitting layer can also be formed by dissolving a binder and a material compound such as a resin in a solvent to form a solution and then thinning it by spin coating or the like. Can be.

When using the compound of this invention for a light emitting layer, you may contain other well-known light emitting materials other than the light emitting material which consists of the aromatic amine derivative of this invention in the light emitting layer in the range which does not impair the objective of this invention, and The light emitting layer containing another well-known light emitting material can also be laminated | stacked on the light emitting layer containing the light emitting material which consists of the aromatic amine derivative of this invention.

The light emitting material used in combination with the compound of the present invention is mainly an organic compound, and examples of the doping material that can be used include, for example, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein and perylene. , Phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, Bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, meloxy Non-imidazole chelated oxynoid compounds, quinacridone, rubrene, fluorescent dyes, and the like, but are not limited thereto.

As a host material which can be used in combination with the compound of this invention, the compound represented by following formula (i)-xi is preferable.

Asymmetric anthracene represented by the following formula (i).

(In Formula (I), Ar is a substituted or unsubstituted condensed aromatic group having 10 to 50 nuclear carbon atoms.

Ar 'is a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.

X is a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon atom 1 to 50 alkoxy groups, substituted or unsubstituted aralkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 50 nuclear atoms, substituted or unsubstituted arylcycles having 5 to 50 nuclear atoms Or an alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxy group.

a, b and c are each an integer of 0-4.

n is an integer of 1-3. In addition, when n is 2 or more, the inside of [] may be same or different.)

Asymmetric monoanthracene derivatives represented by the following formula (ii).

(In Formula (ii), Ar ¹ and Ar ² are each independently a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms, m and n are each an integer of 1 to 4, provided that m = n = 1 and In addition, when the bonding position of Ar ¹ and Ar ^{2 to} the benzene ring is bilaterally symmetric, Ar ¹ and Ar ² are not the same, and when m or n is an integer of 2 to 4, m and n are different integers.

R ¹ to R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted aromatic carbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon atom 1 to A 50-alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted nuclear atom having 5 to 50 atoms Aryloxy group, substituted or unsubstituted arylthio group having 5 to 50 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted silyl group, carboxyl group, halogen atom, between Ano groups, nitro groups, and hydroxyl groups.)

An asymmetric pyrene derivative represented by the following formula (iii).

[In Formula iii, Ar and Ar 'are each a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.

L and L 'are a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluoreneylene group, or a substituted or unsubstituted dibenzosilylene group, respectively.

m is an integer of 0-2, n is an integer of 1-4, s is an integer of 0-2, t is an integer of 0-4.

In addition, L or Ar is bonded to any one of positions 1 to 5 of pyrene, and L 'or Ar' is bonded to any one of positions 6 to 10 of pyrene.

However, when n + t is even, Ar, Ar ', L, and L' satisfy | fill following (1) or (2).

(1) Ar ≠ Ar 'and / or L ≠ L' (where ≠ represents a result of another structure)

(2) When Ar = Ar 'and L = L'

  (2-1) m ≠ s and / or n ≠ t, or

  (2-2) when m = s and n = t,

    (2-2-1) L and L ', or pyrene, are bonded to different binding positions on Ar and Ar', respectively, or (2-2-2) L and L ', or pyrene, Ar and Ar' When bonded to the same bonding position of the phase, the substitution position in the pyrene of L and L 'or Ar and Ar' is not 1, 6, or 2 and 7 positions.]

An asymmetric anthracene derivative represented by the following formula (iv).

(In Formula (iv), A ¹ and A ² are each independently a substituted or unsubstituted condensed aromatic cyclic group having 10 to 20 nuclear carbon atoms.

A ¹ and A ² each independently represent a hydrogen atom or a substituted or unsubstituted aromatic cyclic group having 6 to 50 nuclear carbon atoms.

R ¹ to R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted aromatic carbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted carbon atom 1 to A 50-alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted nuclear atom having 5 to 50 atoms Aryloxy group, substituted or unsubstituted arylthio group having 5 to 50 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted silyl group, carboxyl group, halogen atom, between Anano group, nitro group or hydroxy group.

^Two or more Ar <^1> , Ar <^2> , R <^9> and R <^10> may be sufficient, and may form the saturated or unsaturated cyclic structure between adjacent things.

However, in the general formula (1), groups which become symmetrical with respect to the X-Y axis indicated on the anthracene do not bind to the 9th and 10th positions of the anthracene in the center.)

Anthracene derivative represented by the following formula (v).

(In formula v, R ¹ to R ¹⁰ are each independently hydrogen atom, alkyl group, cycloalkyl group, optionally substituted aryl group, alkoxyl group, aryloxy group, alkylamino group, alkenyl group, arylamino group or substituted. A good heterocyclic group is represented, and a and b each represent an integer of 1 to 5, and when they are 2 or more, each of R ¹ or R ^{2 may} be the same or different in each other, and R ¹ or R good even though the ^two with each other are combined to form a ring, R ³ and R ^4, R ⁵ and R ^6, R ⁷ and R ^8, R ⁹ and R ¹⁰ are good even if they form a ring by combining with each other. L ¹ is a single A bond, -O-, -S-, -N (R)-(R represents an alkyl group or an optionally substituted aryl group), an alkylene group or an arylene group.)

Anthracene derivative represented by the following formula (vi).

(In formula vi, R ¹¹ to R ²⁰ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an arylamino group or a polycyclic group which may be substituted, c, d, e and f represents an integer of 1 to 5, respectively, when they are 2 or more, each other R ^11, each other and each other R ^12, R ¹⁶ together or R ^17, the same or may be to also different in each addition R ¹¹ each other, each other R ^12, to the bond between R ¹⁶ or R ¹⁷ together may even form a ring, and the R ¹³ and R ^14, R ¹⁸ and R ¹⁹ combine with each other is good even if they form a ring. L ² represents a single bond , -O-, -S-, -N (R)-(R represents an alkyl group or an optionally substituted aryl group), an alkylene group or an arylene group.)

Spirofluorene derivative represented by the following formula (vii).

(In Formula vii, A ⁵ to A ⁸ are each independently a substituted or unsubstituted biphenylyl group or a substituted or unsubstituted naphthyl group.)

A condensed ring-containing compound represented by the following formula (viii).

(In the above formula viii, A ⁹ to A ¹⁴ are the same as above, and R ²¹ to R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an alkoxyl group having 1 to 6 carbon atoms. , An aryloxy group having 5 to 18 carbon atoms, an aralkyloxy group having 7 to 18 carbon atoms, an arylamino group having 5 to 16 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms, or a halogen atom, At least one of A ⁹ to A ¹⁴ is a group having three or more condensed aromatic rings.)

A fluorene compound represented by the following general formula (ix).

(In formula ix, R ₁ and R ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, between represents a cyano group or a halogen atom. may be different even if they have the same each other and each other R _1, R ₂ that is bonded to another fluorene, may be different even if the same is R ₁ and R ₂ that is bonded to the same fluorene. R ₃ and R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R ₃ bonded to another fluorene group, R ₄ They may be the same or different, and R <_3> and R <_4> couple | bonded with the same fluorene group may be same or different.Ar <_1> and Ar <_2> are substituted or unsubstituted condensation whose sum total of a benzene ring is three or more. Or a condensed polycyclic heterocyclic group bonded to a fluorene group with a substituted or unsubstituted carbon having a total of three or more ring aromatic groups or a benzene ring and a hetero ring, and Ar ₁ and Ar ₂ may be the same or different. Represents an integer.)

A compound having an anthracene central skeleton represented by the following formula (x).

(In Formula (x), A ₁ and A ₂ are each independently a group derived from a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms. The aromatic ring may be substituted with one or two or more substituents.)

The substituent is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, and a substituted or unsubstituted carbon group having 1 to 50 carbon atoms. 50 alkoxy groups, substituted or unsubstituted aralkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 50 nuclear atoms, substituted or unsubstituted arylthio groups having 5 to 50 nuclear atoms, A substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group and a hydroxyl group.

When the aromatic ring is substituted with two or more substituents, the substituents may be the same or different, and adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure.

R ₁ to R ₈ are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 nuclear atoms, a substituted or unsubstituted carbon number 1 to 50 alkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 50 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted nuclear atoms An aryloxy group having 5 to 50 substituted or substituted or unsubstituted arylthio groups having 5 to 50 nuclear atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group, a carboxyl group, Halogen atom, cyano group, nitro group and hydroxyl group.)

A compound having a structure represented by the following formula (xi) in which A ₁ and A ₂ are different groups in the formula (x).

(In Formula (xi), A and A, R to R are each independently the same as formula (x).

However, the symmetrical groups with respect to the X-Y axis shown on the anthracene do not couple to the 9th and 10th positions of the central anthracene.)

Among the above host materials, preferably an anthracene derivative, more preferably a monoanthracene derivative, and particularly preferably an asymmetric anthracene.

A host suitable for phosphorescence emission which consists of a compound containing a carbazole ring is a compound which has a function which light-emits a phosphorescence compound as a result of energy transfer to a phosphorescence compound from the excited state. The host compound is not particularly limited as long as it is a compound capable of energy transfer of exciton energy to the phosphorescent compound, and can be appropriately selected according to the purpose. You may have arbitrary heterocycles etc. other than a carbazole ring.

Specific examples of such host compounds include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkaine derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, and aryls. Amine derivative, amino substituted chalcone derivative, styryl anthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styryl amine compound, aromatic dimethylidene compound, porphyrin type Heterocyclic tetras such as compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyrylpyrazine derivatives, naphthalene perylenes Carboxylic anhydride, phthalocyanine derivatives, gold of 8-quinolino derivatives Various metal complex polysilane-based compounds, poly (N-vinylcarbazole) derivatives, poly (N-vinylcarbazole) derivatives, aniline copolymers, thiophen oligomers, and polythios represented by complexes, metal phthalocyanines, metal complexes containing benzoxazole or benzothiazole as ligands And high molecular compounds such as conductive polymer oligomers such as offen, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. A host compound may be used independently and may use 2 or more types together.

As a specific example, the following compounds are mentioned.

Phosphorescent dopants are compounds that can emit light from triplet excitons. Although it does not specifically limit, if it emits light from triplet excitons, It is preferable that it is a metal complex containing at least 1 metal chosen from the group which consists of Ir, Ru, Pd, Pt, Os, and Re, A porphyrin metal complex or orthometallization Metal complexes are preferred. As a porphyrin metal complex, a porphyrin platinum complex is preferable. A phosphorescent compound may be used independently and may use 2 or more types together.

There are various ligands for forming an orthometalated metal complex, but preferred ligands include 2-phenylpyridine derivative, 7,8-benzoquinoline derivative, 2- (2-thienyl) pyridine derivative, and 2- (1- Naphthyl) pyridine derivatives, 2-phenylquinoline derivatives, and the like. These derivatives may have a substituent as needed. In particular, a fluoride or trifluoromethyl group is preferably used as a blue dopant. Moreover, you may have ligands other than the said ligands, such as acetylacetonate and a picric acid, as an auxiliary ligand.

There is no restriction | limiting in particular as content in the light emitting layer of a phosphorescent dopant, Although it can select suitably according to the objective, For example, it is 0.1-70 mass%, and 1-30 mass% is preferable. If the content of the phosphorescent compound is less than 0.1% by mass, light emission is weak and the effect thereof is not sufficiently exhibited. If the content of the phosphorescent compound is greater than 70% by mass, a phenomenon called concentration quenching becomes remarkable, and device performance is lowered.

In addition, the light emitting layer may contain a hole transporting material, an electron transporting material, and a polymer binder as necessary.

Moreover, the film thickness of a light emitting layer becomes like this. Preferably it is 5-50 nm, More preferably, it is 7-50 nm, Most preferably, it is 10-50 nm. If the thickness is less than 5 nm, the light emitting layer may be difficult to be formed, and the chromaticity may be difficult to adjust. If the thickness exceeds 50 nm, the driving voltage may increase.

(5) Hole injection and transport layer (hole transport zone)

The hole injection / transport layer is a layer which assists hole injection to the light emitting layer and transports it to the light emitting region, and has a high hole mobility and a small ionization energy of 5.6 eV or less. As such a hole injection / transport layer, a material for transporting holes to the light emitting layer at a lower electric field strength is preferable, and the mobility of holes is, for example, at least 10 ⁻⁴ when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied. It is preferable if it is cm <^2> / V * second.

When the aromatic amine derivative of the present invention is used in the hole transport zone, the hole injection and transport layer may be formed by the aromatic amine derivative of the present invention alone, or may be mixed with other materials and used.

The material for forming the hole injection / transport layer by mixing with the aromatic amine derivative of the present invention is not particularly limited as long as it has the above desirable properties, and is conventionally used as a charge transport material for holes in an optical conductive material, or an organic EL device. Any of the known ones used for the hole injection / transport layer may be selected and used. In this invention, the material which has a hole transport ability and can be used for a hole transport zone is called a hole transport material.

Specific examples include triazole derivatives (see US Pat. No. 3,112,197, etc.), oxadiazole derivatives (see US Pat. No. 3,189,447, etc.), imidazole derivatives (see Japanese Patent Publication No. 37-16096, etc.), polyarylal Kane derivatives (US Pat. Nos. 3,615,402, 3,820,989, 3,542,544, Japanese Patent Publication No. 45-555, 51-10983, Japanese Patent Publication No. 51-93224, 55-17105, 56-4148, 55-108667, 55-156953, 56-36656, etc., pyrazoline derivatives and pyrazolone derivatives (US Pat. No. 3,180,729). 4,278,746, Japanese Patent Laid-Open No. 55-88064, 55-88065, 49-105537, 55-51086, 56-80051, 56-88141 No. 57-45545, No. 54-112637, No. 55-74546, etc.), Nylenediamine derivatives (see US Patent No. 3,615,404, Japanese Patent Publication No. 51-10105, 46-3712, 47-25336, Japanese Patent Publication No. 54-119925, etc.), aryl Amine derivatives (US Pat. Nos. 3,567,450, 3,240,597, 3,658,520, 4,232,103, 4,175,961, 4,012,376, 4,012,376, Japanese Patent Publication No. 49-35702, Japanese Patent Application Laid-Open No. 39-27577, Japanese Patent Application Laid-Open No. 55-144250, Japanese Patent No. 56-119132, Japanese Patent No. 56-22437, West German Patent No. 1,110,518, etc., and an amino substituted chalcone derivative (US Patent No. 3,526,501) Oxazole derivatives (as disclosed in US Pat. No. 3,257,203, etc.), styryl anthracene derivatives (see Japanese Patent Application Laid-Open No. 56-46234, etc.), fluorenone derivatives (Japanese Patent Laid-Open No. 54- 110837, etc.), Hide Razon Derivatives (US Pat. No. 3,717,462, Japanese Patent Application Laid-Open No. 54-59143, 55-52063, 55-52064, 55-46760, 57-11350, 57 -148749, Japanese Patent Laid-Open No. 2-311591, etc., Stilbene derivatives (Japanese Patent Publication No. 61-210363, Japanese Patent Application Laid-Open No. 61-228451, Japanese Patent Application Laid-Open No. 61-14642, Japanese Patent Application Laid-Open No. 61-72255 No. 62-47646, No. 62-36674, No. 62-10652, No. 62-30255, No. 60-93455, No. 60-94462, No. 60-174749 Japanese Patent Application Laid-Open No. 60-175052, etc.), silazane derivatives (US Pat. No. 4,950,950), polysilane-based (Japanese Patent Laid-Open No. 2-204996), aniline copolymers (Japanese Patent Laid-Open No. 2-) 282263) etc. can be mentioned.

Although the above can be used as a material of a hole injection / transport layer, a porphyrin compound (thing disclosed by Unexamined-Japanese-Patent No. 63-295695 etc.), an aromatic tertiary amine compound, and a styrylamine compound (US Pat. No. 4,127,412, Japanese Patent Publication Nos. 53-27033, 54-58445, 55-79450, 55-144250, 56-119132, 61-295558, 61-98353 Japanese Patent Application Laid-Open No. 63-295695, etc.), in particular, it is preferable to use an aromatic tertiary amine compound.

Further, for example, 4,4'-bis (N- (1-naphthyl) -N-phenylamino) biphenyl having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule (hereinafter referred to as "NPD"). 4,4 ', 4 "-tris (N- (3-methylphenyl)-, to which triphenylamine units described in Japanese Patent Application Laid-open No. Hei 4-308688 are connected in three starburst forms. N-phenylamino) triphenylamine (hereinafter abbreviated as "MTDATA"), etc. are mentioned.

In addition, a nitrogen-containing heterocyclic derivative represented by the following chemical formula disclosed in Japanese Patent-3571977 can also be used.

In the formula, R ¹²¹ to R ¹²⁶ represent any one of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and a substituted or unsubstituted heterocyclic group. However, R ¹²¹ to R ¹²⁶ may be the same or different. R ¹²¹ and R ¹²² , R ¹²³ and R ¹²⁴ , R ¹²⁵ and R ¹²⁶ , R ¹²¹ and R ¹²⁶ , R ¹²² and R ¹²³ , and R ¹²⁴ and R ¹²⁵ may form a condensed ring.)

Moreover, the compound of the following formula described in Unexamined-Japanese-Patent No. 2004-0113547 can also be used.

(In the above formula, R ¹³¹ to R ¹³⁶ are substituents, and preferably electron aspiration groups such as cyano group, nitro group, sulfonyl group, carbonyl group, trifluoromethyl group, and halogen.)

As represented by these materials, an acceptor material can also be used as a hole injection material, These specific examples are as above-mentioned.

In addition to the above-described aromatic dimethylidine-based compound as the material of the light emitting layer, inorganic compounds such as p-type Si and p-type SiC can also be used as the material for the hole injection and transport layer.

The hole injection and transport layer can be formed by thinning the aromatic amine derivative of the present invention by a known method such as vacuum deposition, spin coating, casting, or LB. Although the film thickness as a hole injection and transport layer does not have a restriction | limiting in particular, Usually, it is 5 nm-5 micrometers. If the hole injection and transport layer contains the aromatic amine derivative of the present invention in the hole transport zone, the hole injection and transport layer may be composed of one or two or more layers of the above-described materials, and is different from the hole injection and transport layer. The hole injection / transport layer which consists of a compound of the above may be laminated.

In addition, an organic semiconductor layer may be provided as a layer to assist hole injection into the light emitting layer, and it is suitable to have a conductivity of 10 ^-10 S / cm or more. As the material of such an organic semiconductor layer, conductive oligomers such as thiophene-containing oligomers and arylamine-containing oligomers disclosed in JP-A-8-193191, conductive dendrimers such as arylamine-containing dendrimers, and the like can be used.

(6) electron injection and transport layer

Next, the electron injection layer / transport layer is a layer which assists the injection of electrons into the light emitting layer and transports it to the light emitting region, and has a high electron mobility and an adhesion improving layer, particularly a material having good adhesion with the cathode among the electron injection layers. It consists of layers.

In addition, since the light emitted by the organic EL element is reflected by the electrode (in this case, the cathode), it is known that the light emitted directly from the anode and the light emitted via reflection by the electrode interfere with each other. In order to effectively utilize this interference effect, the electron transport layer is appropriately selected from a film thickness of several nm to several μm, but an electric field of 10 ⁴ to 10 ⁶ V / cm is applied to avoid voltage rise, especially when the film thickness is thick. Preferably, the electron mobility is at least 10 ⁻⁵ cm ² / Vs or greater.

As a material used for an electron injection layer, the metal complex and oxadiazole derivative of 8-hydroxyquinoline or its derivative (s) are suitable. As a specific example of the metal complex of the said 8-hydroxyquinoline or its derivative (s), the metal chelate oxynoid compound containing the chelate of auxin (generally 8-quinolino or 8-hydroxyquinoline), for example, tris (8-quinolino) Aluminum can be used as the electron injection material.

On the other hand, as an oxadiazole derivative, the electron transfer compound represented with the following general formula is mentioned.

^{(Wherein, Ar 1, Ar 2, Ar} 3, Ar 5, Ar 6 and Ar ⁹ are each a substituted or non-may be a substituted aryl, each the same even if different from each other. In addition, Ar ^4, Ar ⁷ and Ar ⁸ is Substituted or unsubstituted arylene groups, each of which may be the same or different)

Here, as an aryl group, a phenyl group, biphenylyl group, anthryl group, peryleneyl group, and pyrenyl group are mentioned. Moreover, as an arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthylene group, a peryleneylene group, a pylenylene group, etc. are mentioned. Moreover, as a substituent, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned. It is preferable that this electron transfer compound is thin film formation property.

The following are mentioned as a specific example of the said electron transport compound.

Moreover, as a material used for an electron injection layer and an electron carrying layer, what is represented by following formula (A) -F can also be used.

(A)

(A)

(B)

(B)

(In Formulas A and B, A ¹ to A ³ are each independently a nitrogen atom or a carbon atom.

Ar ¹ is, in the formula (A), a substituted or non-substituted aryl group of nuclei having 6 to 60 carbon atoms, or a substituted or non-substituted nucleus having 3 to 60 heteroaryl group, in formula B Ar ¹ is Ar ¹ of formula A Is a divalent arylene group, Ar ² is a hydrogen atom, substituted or unsubstituted aryl group having 6 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, substituted or unsubstituted carbon number Or an alkyl group of 1 to 20, or a substituted or unsubstituted alkoxy group of 1 to 20 carbon atoms, or a divalent group thereof. Provided that any one of Ar ¹ and Ar ² is a substituted or unsubstituted condensed cyclic group having 10 to 60 carbon atoms, a substituted or unsubstituted monoheterocondensed cyclic group having 3 to 60 carbon atoms, or a divalent group thereof to be.

L ¹ , L ² and L are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms, or a substituted or unsubstituted flu It is an orange.

R is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group A substituted alkoxy group having 1 to 20 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, a plurality of R's may be the same or different, and a plurality of adjacent R groups may be bonded to each other to form a carbocyclic aliphatic ring. Alternatively, a carbocyclic aromatic ring may be formed.

R ¹ is a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted group Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, or -L-Ar ¹ -Ar ² ).

HAr-L-Ar^One-Ar² (C)

(In Formula C, HAr is a C3-40 nitrogen-containing heterocyclic ring which may have a substituent, L is a C6-C60 arylene group which may have a single bond, a substituent, and C3-C20 may have a substituent. 60 heteroaryl group, or even have a substituent fluorenyl group of, Ar ¹ is even have a substituent, and good having 6 to a divalent aromatic hydrocarbon 60 group, Ar ² is even have a substituent having 6 to 60 carbon atoms Nitrogen heterocyclic derivative represented by the aryl group or a heteroaryl group having 3 to 60 carbon atoms which may have a substituent.

(D)

(D)

(In Formula D, X and Y are each independently a saturated or unsaturated hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, hydroxyl group, substituted or unsubstituted aryl group having 1 to 6 carbon atoms, substituted or It is an unsubstituted heterocyclic ring or a structure in which X and Y combine to form a saturated or unsaturated ring, R ₁ to R ₄ are each independently hydrogen, a halogen atom, a substituted or unsubstituted carbon of 1 to 6 Alkyl group, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group , Foam A monocyclic group, an isocyano group, a cyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group or a cyano group, or when adjacent, a substituted or unsubstituted ring is condensed Siraccyclopentadiene derivative represented by the above).

(E)

(E)

(In Formula E, R ₁ to R ₈ , and Z ₂ each independently represent a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic group, a heterocyclic group, a substituted amino group, a substituted boryl group, an alkoxy group, or an aryloxy group, X, Y and Z ₁ each independently represent a saturated or unsaturated hydrocarbon group, aromatic group, heterocyclic group, substituted amino group, alkoxy group or aryloxy group, and the substituents of Z ₁ and Z ₂ are bonded to each other to form a condensed ring Or n represents an integer of 1 to 3, and when n is 2 or more, Z ₁ may be different, provided that n is 1, X, Y and R ₂ are methyl groups, and R ₈ is a hydrogen atom or And a substituted boryl group, and n is 3 and does not include the case where Z ₁ is a methyl group.

(F)

(F)

[In the above formula F, Q ¹ and Q ² each independently represent a ligand represented by the following formula G, L is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, substituted or free Substituted aryl group, substituted or unsubstituted heterocyclic group, -OR ¹ (R ¹ is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted Heterocyclic group) or -O-Ga-Q ³ (Q ⁴ ) (Q ³ and Q ⁴ are the same as Q ¹ and Q ² ).

(G)

(G)

[In Formula (G), rings A ¹ and A ² are condensed 6-membered aryl ring structures which may have a substituent.]

Such a metal complex has strong properties as an n-type semiconductor and has high electron injection ability. Moreover, since the formation energy at the time of complex formation is also low, the binding property of metal and ligand of the formed metal complex is also strengthened, and the fluorescence quantum efficiency as a light emitting material is also increasing.

Specific examples of the substituents of the rings A ¹ and A ² forming the ligand of the formula G include chlorine, bromine, iodine, halogen atoms of fluorine, methyl group, ethyl group, propyl group, butyl group, s-butyl group, t- Substituted or unsubstituted alkyl groups such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, phenyl group, naphthyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-fluoro Substituted or unsubstituted aryl groups, such as a phenyl group, 3-trichloromethylphenyl group, 3-trifluoromethylphenyl group, and 3-nitrophenyl group, a methoxy group, n-butoxy group, t-butoxy group, and trichloromethoxy group , Trifluoroethoxy group, pentafluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1,1,3,3,3-hexafluoro-2-propoxy A substituted or unsubstituted alkoxy group, such as 6- (perfluoroethyl) hexyloxy group, phenoxy group, p-nitrophenoxy group, pt-butylphenoxy group, 3 Substituted or unsubstituted aryloxy groups such as fluorophenoxy group, pentafluorophenyl group, and 3-trifluoromethylphenoxy group, methylthio group, ethylthio group, t-butylthio group, hexylthio group, octylthio group Substituted or unsubstituted alkylthio groups, phenylthio groups, p-nitrophenylthio groups, pt-butylphenylthio groups, 3-fluorophenylthio groups, pentafluoro Substituted or unsubstituted arylthio groups, such as phenylthio group and 3-trifluoromethylphenylthio group, cyano group, nitro group, amino group, methylamino group, diethylamino group, ethylamino group, diethylamino group, dipropylamino group Mono or di-substituted amino groups such as dibutylamino group, diphenylamino group, bis (acetoxymethyl) amino group, bis (acetoxyethyl) amino group, bis (acetoxypropyl) amino group, bis (Acetoxybutyl) Acylamino groups, such as an amino group, a hydroxyl group, a siloxy group, an acyl group, a methyl carbamoyl group, a dimethyl carbamoyl group, an ethyl carbamoyl group, a diethyl carbamoyl group, a propylcarbamoyl group, and a butylca Cycloalkyl groups, such as a carbamoyl group, a carboxylic acid group, a sulfonic acid group, an imide group, a cyclopentane group, and a cyclohexyl group, such as a night oil group and a phenyl carbamoyl group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group Aryl groups such as fluorenyl group, pyrenyl group, pyridinyl group, pyrazineyl group, pyrimidinyl group, pyridazineyl group, triazineyl group, indolinyl group, quinolineyl group, acridinyl group, pyrrolidinyl group, dioxanyl group . Piperizine group, morpholigin group, piperazine group, triatinyl group, carbazolyl group, furanyl group, thiophenyl group, oxazolyl group, oxadiazolyl group, benzooxazolyl group, thiazolyl group, thiadiazole Heterocyclic groups such as diary, benzothiazolyl group, triazolyl group, imidazolyl group, benzoimidazolyl group, and furanyl group. Further, the above substituents may be bonded to further form a 6-membered aryl ring or hetero ring.

In a preferred embodiment of the organic EL device of the present invention, there is an element containing a reducing dopant in a region for transporting electrons or in an interface region between the cathode and the organic layer. Here, the reducing dopant is defined as a substance capable of reducing the electron transporting compound. Therefore, various materials can be used as long as they have a constant reducing property. For example, alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, At least one substance selected from the group consisting of oxides of rare earth metals or halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be suitably used.

More specifically, preferred reducing dopants include Li (work function: 2.9 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), and Cs (work At least one alkali metal selected from the group consisting of 1.95 eV) or Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV) Particularly preferred are those having a work function of 2.9 eV or less, which may include at least one alkaline earth metal selected from. Of these, the more preferred reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, most preferably Cs. In particular, these alkali metals have high reducing ability, and the addition of a relatively small amount of the alkali metal into the electron injection region improves the luminescence brightness and extends the life of the organic EL device. Moreover, as a reducing dopant having a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferable, and in particular, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb or Cs and Na and K It is preferable that it is a combination with. By including Cs in combination, the reduction ability can be exhibited efficiently, and the addition to the electron injection region is expected to improve the emission luminance and increase the life of the organic EL device.

In the present invention, an electron injection layer made of an insulator or a semiconductor may be further provided between the cathode and the organic layer. At this time, the current leakage can be effectively prevented to improve the electron injection property. As such an insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, halides of alkali metals and halides of alkaline earth metals. If an electron injection layer is comprised with these alkali metal chalcogenides, it is preferable at the point which can improve electron injection property. Specifically, preferred alkali metal chalcogenides include, for example, Li ₂ O, K ₂ O, Na ₂ S, Na ₂ Se, and Na ₂ O, and preferred alkali earth metal chalcogenides include, for example, CaO, BaO, SrO, BeO, BaS and CaSe. In addition, examples of the halide of a preferred alkali metal include LiF, NaF, KF, LiCl, KCl, NaCl and the like. Also, as the preferred alkaline earth metal halides of, for example, CaF _2, BaF _2, SrF _2, MgF _2, and there may be mentioned fluorine, or halide other than fluoride such as BeF _2.

Moreover, as a semiconductor which comprises an electron carrying layer, oxide, nitride which contains at least 1 element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn Or 1 type single or 2 types or more combinations, such as oxynitride, are mentioned. Moreover, it is preferable that the inorganic compound which comprises an electron carrying layer is a microcrystalline or amorphous insulating thin film. If the electron transporting layer is composed of these insulating thin films, a more homogeneous thin film is formed, so that pixel defects such as dark spots can be reduced. On the other hand, as such an inorganic compound, the above-mentioned alkali metal chalcogenide, alkaline earth metal chalcogenide, the halide of an alkali metal, the halide of an alkali earth metal, etc. are mentioned.

(7) cathode

As the cathode, in order to inject electrons into the electron injection / transport layer or the light emitting layer, a metal having a low work function (4 eV or less), an alloy, an electrically conductive compound, and a mixture thereof is used as an electrode material. Specific examples of such electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium-silver alloys, aluminum / aluminum oxides, aluminum-lithium alloys, indium, rare earth metals, and the like.

Such a cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

In the case where the light emission from the light emitting layer is taken out from the cathode, it is preferable that the transmittance of the cathode from light emission is greater than 10%.

In addition, the sheet resistance as the cathode is preferably several hundred? /? Or less, and the film thickness is usually 10 nm to 1 m, preferably 50 to 200 nm.

(8) insulation layer

Since an organic EL element applies an electric field to an ultra-thin film, pixel defects due to leakage or a short circuit are likely to occur. In order to prevent this, it is preferable to insert an insulating thin film layer between a pair of electrodes.

Examples of the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, Boron nitride, molybdenum oxide, ruthenium oxide, vanadium oxide, and the like, and mixtures and laminates thereof can be used.

(9) Manufacturing Method of Organic EL Device

According to the material and formation method illustrated above, an organic electroluminescent element can be manufactured by forming an anode, a light emitting layer, a hole injection / transport layer as needed, and an electron injection / transport layer as needed, and forming a cathode thereon. Moreover, it is also possible to manufacture an organic electroluminescent element from a cathode to an anode in the reverse order.

Hereinafter, the manufacturing example of the organic electroluminescent element of the structure by which the anode / hole injection layer / light emitting layer / electron injection layer / cathode were provided in order on the translucent board | substrate is described.

First, a thin film made of an anode material is formed on a suitable light-transmissive substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm. Next, a hole injection layer is provided on this anode. As described above, the hole injection layer can be formed by a vacuum deposition method, a spin coating method, a casing method, an LB method, etc., but a homogeneous film is easy to be obtained, and pinholes are less likely to occur. It is preferable to form by the vacuum vapor deposition method. When the hole injection layer is formed by a vacuum deposition method, the deposition conditions vary depending on the compound (material of the hole injection layer) used, the crystal structure or the recombination structure of the target hole injection layer, and the like. It is preferable to select suitably in the range of 450 degreeC, the degree of vacuum 10 ^{-7-10 -3} Torr, the deposition rate 0.01-50 nm / sec, substrate temperature -50-300 degreeC, and film thickness of 5 nm-5 micrometers.

Next, the formation of the light emitting layer on which the light emitting layer is provided on the hole injection layer is also formed by thinning the organic light emitting material by a method such as vacuum deposition, sputtering, spin coating, casting or the like using a desired organic light emitting material. Although a homogeneous film | membrane is easy to obtain and a pinhole is hard to generate | occur | produce, it is preferable to form by the vacuum evaporation method. When forming a light emitting layer by a vacuum vapor deposition method, although the vapor deposition conditions change with the compound used, it can generally select from the range of conditions like a hole injection layer.

Next, an electron injection layer is provided on this light emitting layer. It is preferable to form by vacuum evaporation method in order to obtain a homogeneous film | membrane like a hole injection layer and a light emitting layer. Deposition conditions can be selected from the range of conditions, such as a hole injection layer and a light emitting layer.

The aromatic amine derivative of the present invention varies depending on which layer of the emission zone or the hole transport zone is included. However, when the vacuum deposition method is used, co-deposition with other materials can be performed. In addition, when using a spin coating method, it can contain by mixing with another material.

Finally, the cathode can be laminated to obtain an organic EL device.

The cathode is made of a metal, and vapor deposition and sputtering can be used. However, in order to protect the underlayer organic material layer from damage at the time of film forming, the vacuum evaporation method is preferable.

It is preferable to produce this organic electroluminescent element from an anode to a cathode consistently with one vacuum suction.

The formation method of each layer of the organic electroluminescent element of this invention is not specifically limited. The formation method by a conventionally well-known vacuum vapor deposition method, a spin coating method, etc. can be used. The organic thin film layer containing the compound represented by the formula (1) used in the organic EL device of the present invention may be vacuum deposition, molecular beam deposition (MBE) or dipping of a solution dissolved in a solvent, spin coating, casting, or bar coating. It can form by a well-known method by the apply | coating methods, such as a method and a roll coating method.

Although the film thickness of each organic layer of the organic electroluminescent element of this invention is not specifically limited, Generally, when a film thickness is too thin, defects, such as a pinhole, are easy to produce, On the contrary, when too thick, a high applied voltage is required and efficiency becomes bad, Usually, the range of several nm to 1 micrometer is preferable.

On the other hand, when a direct current voltage is applied to the organic EL element, light emission is observed when the anode is set to the polarity of + and the cathode is-and the voltage of 5 to 40 V is applied. In addition, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. In addition, when an alternating voltage is applied, uniform light emission is observed only when the anode becomes + and the cathode becomes-. The waveform of the alternating current to be applied may be any.

Hereinafter, the present invention will be described in more detail according to synthesis examples and examples.

The structural formulas of the intermediates 1 to 17 prepared in Synthesis Examples 1 to 17 are as follows.

Synthesis Example 1 (Synthesis of Intermediate 1)

In a 1000 mL three-necked flask under argon, 47 g of 4-bromobiphenyl, 23 g of iodine, 9.4 g of diiodic dihydrate, 42 mL of water, 360 mL of acetic acid, 11 mL of sulfuric acid, and stirred at 65 ° C. for 30 minutes Was reacted at 90 ° for 6 hours. The reaction was poured into iced water and filtered. After washing with water, 67 g of white powder was obtained by washing with methanol. Since intermediate peaks of m / z = 358 and 360 were obtained for C ₁₂ H ₁₅ BrI = 359 by analysis of FD-MS (Desorption Mass Spectrometer), intermediate 1 was identified.

Synthesis Example 2 (Synthesis of Intermediate 2)

10 g of p-terphenyl, 12 g of iodine, 4.9 g of diiodic acid dihydrate, 4.9 g of water, 20 mL of acetic acid and 22 mL of sulfuric acid were added to a 300 mL three-necked flask under argon, and stirred at 65 ° C. for 30 minutes. The reaction was carried out at 90 ° for 6 hours. The reaction was poured into iced water and filtered. After washing with water, 18g of white powder was obtained by washing with methanol. Since FD-MS (desorption mass spectrometry) of jyeotgi, C ₁₈ H ₁₂ with respect to I = 482, m / z = 482 main peak is obtained by the analysis of the powder was identified as Intermediate 2.

Synthesis Example 3 (Synthesis of Intermediate 3)

Under argon stream, 750 g of phenylboronic acid, 900 g of 2-bromothiophene, 142 g of tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ in a 50 L reaction vessel, 2 M sodium carbonate (Na ₂ CO) ₃ ) After 9L of solution and 15L of dimethoxyethane were added, the mixture was reacted at 80 ° C for 8 hours. The reaction solution was extracted with toluene / water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and the crude product obtained was subjected to column purification to obtain 708 g of white powder.

Into a 20 L reaction vessel under argon, 708 g of the compound obtained above and 8 L of N, N-dimethylformamide (DMF) were added, followed by slowly adding 960 g of N-bromosuccinimide (NBS) at room temperature. The reaction was carried out for 12 hours. Extracted with hexane / water and dried over anhydrous sodium sulfate. This was concentrated under reduced pressure, and the crude product obtained was subjected to column purification to obtain 632 g of white powder. The intermediate body 3 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 4 (Synthesis of Intermediate 4)

632 g of intermediate 3 and 7 L of dehydrated tetrahydrofuran (THF) were added to 20 L of reaction vessels under argon airflow, and it cooled to -30 degreeC. 2.3 L of n-butyllithium (n-BuLi, 1.6 M hexane solution) was put, and it was made to react for 1 hour. After cooling to -70 ° C, 1658 g of boric acid triisopropyl ester (manufactured by Tokyo Kasei Co., Ltd.) was added thereto. It heated up slowly and stirred at room temperature for 1 hour. 1.7 L of 10% hydrochloric acid solution was added and stirred. Extraction was performed with ethyl acetate and water, and the organic layer was washed with water. It dried with anhydrous sodium sulfate, and the solvent was distilled off. 330g of white powder was obtained by washing with hexane.

Under argon, in a 20 L reaction vessel, 466 g of 5-phenyl-2-thiophenic boronic acid obtained above, 600 g of 4-iodobromobenzene, tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), 41 g of 2 M sodium carbonate (Na ₂ CO ₃ ) solution, 2.6 L and dimethoxyethane 10 L was added, and then reacted at 80 ° C. for 8 hours. The reaction solution was extracted with toluene / water and dried over anhydrous sodium sulfate. This was concentrated under reduced pressure, and the crude product obtained was subjected to column purification to obtain 263 g of white powder. The intermediate body 4 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 5 (Synthesis of Intermediate 5)

In the synthesis of Intermediate 4, the reaction was carried out in the same manner as in the synthesis of Intermediate 4 except that 4-iodobromobenzene was used as Intermediate 1, 274 g of a white powder was obtained. The intermediate body 5 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 6 (Synthesis of Intermediate 6)

Under argon stream, 5.5 g of aniline, 14.9 g of intermediate 4, 6.8 g of t-butoxy sodium (manufactured by Hiroshima Wako Corporation), tris (dibenzylideneacetone) dipalladium (0) 0.46 g (manufactured by Aldrich Corporation), and 300 mL of dehydrated toluene was put and made to react at 80 degreeC for 8 hours.

After cooling, 500 mL of water was added, the mixture was filtered through Celite, the filtrate was extracted with toluene and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the crude product obtained was purified by column, recrystallized with toluene, collected by filtration and dried to give 8.6 g of pale yellow powder. The intermediate body 6 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 7 (Synthesis of Intermediate 7)

Under argon flow, 185 g of acetoamide (manufactured by Tokyo Kasei Co., Ltd.), 300 g of intermediate 4 (made by Wako Pure Chemical), 544 g of potassium carbonate (made by Wako Pure Chemical), 12.5 g of copper powder (made by Wako Pure Chemical) and decalin 2L Was added and reacted at 190 ° C. for 4 days. After the reaction, the mixture was cooled, 2L of toluene was added, and an insoluble component was collected by filtration. The filtrate was dissolved in 4.5 L of chloroform, and the insolubles were removed and concentrated by activated carbon treatment. Acetone 3L was added to this, and 165g of precipitates were collected by filtration.

This was suspended in 5 L of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 mL of water, and 210 g of an 85% potassium hydroxide aqueous solution was added, followed by reaction at 120 ° C for 8 hours. After the reaction, the reaction solution was poured into 10 L of water, and the precipitate was collected by filtration and washed with water and methanol. The obtained crystals were dissolved in 3 L of tetrahydrofuran, concentrated after treatment with activated carbon, and acetone was added to precipitate the crystals. This was collected by filtration to obtain 127 g of white powder. The intermediate body 7 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 8 (Synthesis of Intermediate 8)

Under argon flow, 185 g of acetoamide (made by Tokyo Kasei Co., Ltd.), 253 g of 4-bromobiphenyl (made by Wako Pure Chemical), 544 g of potassium carbonate (made by Wako Pure Chemical), 12.5 g of copper powder (made by Wako Pure Chemical) and De 2L of karin was thrown in and it was made to react at 190 degreeC for 4 days. After the reaction, the mixture was cooled, 2L of toluene was added, and the insolubles were collected by filtration. The filtrate was dissolved in 4.5 L of chloroform, and the insolubles were removed and concentrated by activated carbon treatment. 3 L of acetone was added to this, and the precipitate was collected by 205 g filtration.

To this, 168 g of Intermediate 4 (made by Wako Pure Chemical), 380 g of potassium carbonate (made by Wako Pure Chemical), 8.8 g of copper powder (made by Wako Pure Chemical) and 2L of decarin were added and reacted at 190 ° C for 4 days. After the reaction, the mixture was cooled, 1.4L of toluene was added, and the insolubles were collected by filtration. The filtrate was dissolved in 3 L of chloroform to remove insoluble content, and then treated with activated carbon and concentrated. Acetone 3L was added to this, and 224g of precipitates were collected by filtration. This was suspended in 3.5 L of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 35 mL of water, and after adding 147 g of an aqueous 85% potassium hydroxide solution, the mixture was reacted at 120 ° C for 8 hours. After the reaction, the reaction solution was poured into 10 L of water, and the precipitate was collected by filtration and washed with water and methanol. The obtained crystals were dissolved in 3 L of tetrahydrofuran by heating, concentrated after treatment with activated carbon, and acetone was added to precipitate crystals. This was collected by filtration to obtain 121 g of white powder. The intermediate body 8 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 9 (Synthesis of Intermediate 9)

In the synthesis of the intermediate 7, the reaction was carried out in the same manner except that the intermediate 4 was changed from 300 g to 600 g, thereby obtaining 212 g of a white powder. The intermediate body 9 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 1O (Synthesis of Intermediate 1O)

In the synthesis of the intermediate 8, the reaction was carried out in the same manner except that 1-bromonaphthalene was used instead of 4-bromobiphenyl, and 9.2 g of white powder was obtained. Column purification was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 11 (Synthesis of Intermediate 11)

Under argon flow, 185 g of acetoamide (manufactured by Tokyo Kasei Co., Ltd.), 300 g of intermediate 4 (made by Wako Pure Chemical), 544 g of potassium carbonate (made by Wako Pure Chemical), 12.5 g of copper powder (made by Wako Pure Chemical) and 2L decalin It injected | thrown-in and reacted at 190 degreeC for 4 days. After the reaction, the mixture was cooled, 2L of toluene was added, and the insolubles were collected by filtration. The filtrate was dissolved in 4.5 L of chloroform, and the insolubles were removed and concentrated by activated carbon treatment. Acetone 3L was added to this, and 165g of precipitates were collected by filtration.

120 g of 4,4'-daiiobibiphenyl (made by Wako Pure Chemical), 163 g of potassium carbonate (produced by Wako Pure Chemical), 3.8 g of copper powder (made by Wako Pure Chemical) and 600 mL of decarin were added thereto, and 4 at 190 ° C. It was reacted for a day.

After the reaction, the mixture was cooled, 600 mL of toluene was added, and the insolubles were collected by filtration. The collected filtrate was dissolved in 1.4 L of chloroform, the insoluble content was removed, and then activated carbonized and concentrated. 1 L of acetone was added to this, and 361 g of filtration collected and precipitated.

This was suspended in 1.5 L of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 mL of water, and 44 g of an 85% potassium hydroxide aqueous solution was added, followed by reaction at 120 ° C for 8 hours. After the reaction, the reaction solution was poured into 10 L of water, and the precipitate was collected by filtration and washed with water and methanol. The obtained crystals were dissolved in 1 L of tetrahydrofuran by heating, concentrated after treatment with activated carbon, and acetone was added to precipitate crystals. This was collected by filtration to obtain 107 g of white powder. The intermediate body 11 was identified by analysis of FD-MS (Desorption Mass Spectrometry).

Synthesis Example 12 (Synthesis of Intermediate 12)

Under argon flow, 1-acetoamide naphthalene 547 g (made by Tokyo Kasei Co., Ltd.), 4,4'- diiodobiphenyl 400 g (made by Wako Pure Chemical), 544 g of potassium carbonate (made by Wako Pure Chemical), 12.5 g of copper powder (Wako Pure Chemical) Co., Ltd. product) and 2L of decalin were added and reacted at 190 ° C for 4 days.

After the reaction, the mixture was cooled, 2L of toluene was added, and the insolubles were collected by filtration. The filtrate was dissolved in 4.5 L of chloroform, and the insolubles were removed and concentrated by activated carbonization. To this was added 3 L of acetone and 382 g of the precipitate was collected by filtration. This was suspended in 5 L of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 mL of water, and 145 g of an 85% potassium hydroxide aqueous solution was added and then reacted at 120 ° C for 8 hours. After the reaction, the reaction solution was poured into 10 L of water, and the precipitate was collected by filtration and washed with water and methanol. The obtained crystals were dissolved in 3 L of tetrahydrofuran by heating, concentrated after treatment with activated carbon, and acetone was added to precipitate the crystals. This was collected by filtration to give 264 g of white powder. The intermediate body 12 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 13 (Synthesis of Intermediate 13)

Under argon stream, 5.1 g of diphenylamine, 10.8 g of intermediate 1, 3 g of t-butoxy sodium (manufactured by Hiroshima Wako Corp.), 0.5 g of bis (triphenylphosphine) palladium (II) chloride (manufactured by Tokyo Kasei Co., Ltd.) And 500 mL of xylene was put and reacted at 130 degreeC for 24 hours.

After cooling, 1000 mL of water was added, the mixture was filtered through Celite, the filtrate was extracted with toluene, and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and the crude product obtained was purified by column, recrystallized with toluene, collected by filtration, and dried to yield 3.4 g of pale yellow horse. The intermediate body 13 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 14 (Synthesis of Intermediate 14)

In the synthesis of the intermediate 13, the reaction was carried out in the same manner as in the case of using 4-iodobromobenzene instead of the intermediate 1 to obtain 2.8 g of a white powder. The intermediate body 14 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 15 (Synthesis of Intermediate 15)

Into a 200 mL three-necked flask, 20.0 g of 4-bromobiphenyl (manufactured by Tokyo Kasei Co., Ltd.), 8.64 g of t-butoxy sodium (manufactured by Wako Pure Chemical) and 84 mg of palladium acetate (manufactured by Wako Pure Chemical) were placed. In addition, agitator was added, rubber caps were set at both sides of the flask, a reflux pipe at the central inlet, a balloon filled with cubic cock and argon gas thereon, and the inside of the balloon was heated three times using a vacuum pump. Substituted with argon gas.

Next, 120 mL of dehydrated toluene (manufactured by Hiroshima Wako Co., Ltd.), 4.08 mL benzylamine (manufactured by Tokyo Kasei Co., Ltd.), and 338 μl of tris-t-butylphosphine (manufactured by Aldrich Co. It added and stirred at room temperature for 5 minutes. Next, the flask was set in an oil bath, and the solution was gradually heated to 120 ° C while stirring. After 7 hours, the flask was removed from the oil bath to terminate the reaction, and left to stand in an argon atmosphere for 12 hours. The reaction solution was transferred to a separating lot, 600 mL of dichloromethane was added to dissolve the precipitate, washed with 120 mL of saturated brine, and the organic layer was dried over anhydrous potassium carbonate. The solvent of the organic layer obtained by filtering potassium carbonate was distilled off, 400 mL of toluene and 80 mL of ethanol were added to the obtained residue, the drying tube was attached, it heated at 80 degreeC, and the residue was melt | dissolved completely. Then, it was left to stand for 12 hours and recrystallized by slow cooling to room temperature. The precipitated crystals were separated by filtration and dried in vacuo at 60 ° C to obtain 13.5 g of N, N-di- (4-biphenylyl) -benzylamine. 1.35 g of N, N-di- (4-biphenylyl) -benzylamine and 135 mg of palladium-activated carbon (10 wt. 100 mL and 20 mL of ethanol were added and dissolved. Next, after putting a stirrer into the flask, a cubic cock equipped with a balloon filled with 2 L of hydrogen gas was attached to the flask, and the inside of the flask system was replaced with hydrogen gas 10 times using a vacuum pump. The reduced hydrogen gas was freshly charged, the volume of hydrogen gas was again 2 L, and the solution was vigorously stirred at room temperature. After stirring for 30 hours, 100 mL of dichloromethane was added, and the catalyst was filtered off. Next, the obtained solution was transferred to a separating lot, washed with 50 mL of saturated aqueous sodium hydrogen carbonate solution, and then the organic layer was separated and dried over anhydrous potassium carbonate. After filtration, the solvent was distilled off, 50 mL of toluene was added to the obtained residue, and it recrystallized. The precipitated crystals were separated by filtration and 0.99 g of di-4-biphenylylamine was obtained by vacuum drying at 50 ° C.

10 g of di-4-biphenylylamine, argon stream, 9.7 g of 4,4'- dibromobiphenyl (made by Tokyo Kasei Co., Ltd.), 3 g of t-butoxy sodium (made by Hiroshima Wako Co., Ltd.), bis (triphenyl force) Fin) Palladium (II) 0.5g (made by Tokyo Kasei Co., Ltd.) and 500 mL of xylene were put, and it reacted at 130 degreeC for 24 hours. 1000 mL of water was added after cooling, the mixture was filtered through Celite, the filtrate was extracted with toluene, and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and the crude product obtained was purified by column, recrystallized with toluene, collected by filtration, and dried to give 9.1 g of 4'-bromo-N, N-dibiphenylyl-4-. Amino-1,1'-biphenyl (intermediate 15) was obtained.

The structural formulas of the compounds H1 to H16 which are the aromatic amine derivatives of the present invention prepared in Synthesis Examples 1 to 15 are as follows.

Synthesis Example 1 (Synthesis of Compound H1)

Under argon stream, 3.4 g of N, N'- diphenylbendiazine, 6.3 g of Intermediate 4, 2.6 g of t-butoxy sodium (manufactured by Hiroshima Wako), tris (dibenzylideneacetone) dipalladium (0) 92 mg (manufactured by Aldrich), 42 mg of tri-t-butylphosphine and 100 mL of dehydrated toluene were added and reacted at 80 ° C. for 8 hours.

After cooling, 500 mL of water was added, the mixture was filtered through Celite, the filtrate was extracted with toluene, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the crude product obtained was purified by column, recrystallized from toluene, collected by filtration and dried to give 3.2 g of pale yellow powder. The compound H1 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 2 (Synthesis of Compound H2)

Under argon, 4.1 g of 4,4'- diiodobiphenyl, 8.1 g of intermediate 8, 2.6 g of t-butoxy sodium (made by Hiroshima Wako Corp.), tris (dibenzylidene acetone) dipalladium (0) 92 mg (Aldrich), 42 mg of tri-t-butylphosphine and 100 mL of dehydrated toluene were added and reacted at 80 ° C for 8 hours.

After cooling, 500 mL of water was added, the mixture was filtered through Celite, the filtrate was extracted with toluene, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the crude product obtained was column purified, recrystallized with toluene, collected by filtration and dried to give 3.9 g of pale yellow powder. The compound H2 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 3 (Synthesis of Compound H3)

In Synthesis Example 1, the reaction was carried out in the same manner except that 4.4 g of Intermediate 12 was used instead of N, N'-diphenylbendiazine, and thus 5.1 g of pale yellow powder was obtained. The compound H3 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 4 (Synthesis of Compound H4)

In Synthesis Example 1, the reaction was carried out in the same manner except that 7.8 g of Intermediate 5 was used instead of Intermediate 4, and 4.7 g of a pale yellow powder was obtained. The compound H4 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 5 (Synthesis of Compound H5)

Under argon stream, 7.7 g of intermediate 8, 11.0 g of intermediate 15, 2.6 g of t-butoxy sodium (manufactured by Hiroshima Wako Corp.), tris (dibenzylideneacetone) dipalladium (0) 92 mg (manufactured by Aldrich Corporation), 42 mg of tri-t-butylphosphine and 100 mL of dehydrated toluene were added and reacted at 80 degreeC for 8 hours.

After cooling, 500 mL of water was added, the mixture was filtered through Celite, the filtrate was extracted with toluene, and dried over anhydrous magnesium sulfate. It was concentrated under reduced pressure, and the crude product obtained was purified by column, recrystallized from toluene, collected by filtration and dried to give 9.1 g of pale yellow powder. The compound H5 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 6 (Synthesis of Compound H6)

In Synthesis Example 5, the reaction was carried out in the same manner as in the procedure of 6.2 g of Intermediate 6 instead of Intermediate 8, whereby 6.1 g of pale yellow powder was obtained. The compound H6 was identified by analysis of FD-MS (Desorption Mass Spectrometry).

Synthesis Example 7 (Synthesis of Compound H7)

In Synthesis Example 5, the reaction was carried out in the same manner as in the case of using 7.2 g of Intermediate 10 instead of Intermediate 8, thereby obtaining 5.5 g of pale yellow powder. The compound H7 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 8 (Synthesis of Compound H8)

In Synthesis Example 5, the reaction was carried out in the same manner except that 9.1 g of Intermediate 9 was used instead of Intermediate 8, thereby obtaining 7.2 g of a pale yellow powder. The compound H8 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 9 (Synthesis of Compound H9)

In Synthesis Example 2, the reaction was carried out in the same manner except that 9.5 g of Intermediate 9 was used instead of Intermediate 8, and thus 4.1 g of pale yellow powder was obtained. The compound H9 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 10 (Synthesis of Compound H10)

In Synthesis Example 2, the reaction was carried out in the same manner except that 4.8 g of Intermediate 2 and 6.5 g of Intermediate 6 instead of Intermediate 8 were used instead of 4,4'-diiodobiphenyl to obtain 3.2 g of pale yellow powder. . The compound H10 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 11 (Synthesis of Compound H11)

In Synthesis Example 2, the reaction was carried out in the same manner except that 3.3 g of 1,4-dioiodobenzene was used instead of 4,4'-diiodobiphenyl and 6.5 g of Intermediate 6 instead of Intermediate 8 was 2.5 g. A pale yellow powder of was obtained. The compound H11 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 12 (Synthesis of Compound H12)

In Synthesis Example 2, 3.5g of 2,7-dibromo-9,9-dimethylfluorene and 6.5g of intermediate 6 instead of intermediate 8 were used instead of 4,4'-diiodobiphenyl. As a result of the reaction, 3.1 g of pale yellow powder was obtained. The compound H12 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 13 (Synthesis of Compound H13)

In Synthesis Example 1, the reaction was carried out in the same manner as in the case of using 2.3 g of Intermediate 7 instead of N, N'-diphenylbendizin and 8.0 g of Intermediate 13 instead of Intermediate 4. As a result, 19 g of pale yellow powder was obtained. . The compound H13 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 14 (Synthesis of Compound H14)

In Synthesis Example 1, the reaction was carried out in the same manner as in the case of using 6.2 g of Intermediate 11 instead of N, N'-diphenylbendiazine and 8.0 g of Intermediate 13 instead of Intermediate 4, to obtain 6.2 g of pale yellow powder. did. The compound H14 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 15 (Synthesis of Compound H15)

In Synthesis Example 1, the reaction was carried out in the same manner except that 6.5 g of Intermediate 11 was used instead of N, N'-diphenylbendizin and 6.5 g of Intermediate 14 instead of Intermediate 4, and thus 4.1 g of pale yellow powder was obtained. Obtained. The compound H18 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Synthesis Example 16 (Synthesis of Compound H16)

In Synthesis Example 1, the reaction was carried out in the same manner except that 9.3 g of Intermediate 6 was used instead of 4,4'-diiodobiphenyl and 4.8 g of Tris (4-bromophenyl) amine was used instead of Intermediate 12. g pale yellow powder was obtained. The compound H16 was identified by analysis of FD-MS (Desorption Mass Spectrometer).

Example 1 (Manufacture of Organic EL Device)

A glass substrate with a transparent ITO transparent electrode (manufactured by Geomatic Co., Ltd.) having a thickness of 25 mm x 75 mm x 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, followed by UV ozone cleaning for 30 minutes.

The glass substrate with a transparent electrode line after cleaning was attached to the substrate holder of a vacuum deposition apparatus, and the said compound H1 film | membrane of a film thickness of 60 nm was formed into a film by covering the said transparent electrode on the surface of the side in which the transparent electrode line is formed first. This H1 film functions as a hole injection layer. The following compound layer TBDB with a film thickness of 20 nm was formed on this H1 film. This membrane functions as a hole transport layer. The following compound EM1 with a film thickness of 40 nm was deposited thereon and formed into a film. At the same time, the amine compound D1 having the following styryl group was deposited as a light emitting molecule such that the weight ratio of EM1 and D1 was 40: 2. This film functions as a light emitting layer.

The following Alq film | membrane with a film thickness of 10 nm was formed into this film. This functions as an electron injection layer. Then, Li (Li source: manufactured by Sas Getter Co., Ltd.) and Alq, which are the next reducing dopant, were deposited by binary to form an Alq: Li film (film thickness of 10 nm) as an electron injection layer (cathode). Metal Al was deposited on the Alq: Li film to form a metal cathode, thereby forming an organic EL device.

In addition, the luminous efficiency was measured about the obtained organic electroluminescent element, and the luminous color was observed. The luminous efficiency measured luminance using the Minolta CS1000, and computed the luminous efficiency in 10 mA / cm <^2> . Table 1 shows the results of measuring the half-life of light emission in the initial luminance of 5000 cd / m ² , room temperature, and DC constant current driving.

Examples 2 to 4 (Manufacture of Organic EL Device)

In Example 1, an organic EL device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of the compound H1 as the hole transport material.

Table 1 shows the results of measuring the luminous efficiency of the obtained organic EL device, observing the luminous color, and measuring the half-life of light emission at initial luminance of 5000 cd / m ² , room temperature, and DC constant current driving.

Comparative Example 1

In Example 1, the organic EL device was produced in the same manner as in Comparative Example 1 except that Compound H1 was used as the hole transporting material.

Table 1 shows the results of measuring the luminous efficiency of the obtained organic EL device, observing the luminous color, and measuring the half-life of light emission at initial luminance of 5000 cd / m ² , room temperature, and DC constant current driving.

Example Hole transport material Voltage (V) Luminous color Half-life (h) One H1 6.3 blue 380 2 H3 6.2 blue 320 3 H5 6.5 blue 350 4 H6 6.4 blue 340 5 H1 6.4 blue 370 Comparative Example 1 Comparative Compound 1 7.1 blue 280 Comparative Example 2 Comparative Compound 1 7.0 blue 270

Example 5 (Manufacture of Organic EL Device)

In Example 1, the organic EL element was produced similarly except having used the following arylamine compound D2 instead of the amine compound D1 which has a styryl group. Me is a methyl group.

Table 1 shows the results of measuring the luminous efficiency of the obtained organic EL device, observing the luminous color, and measuring the half-life of light emission at initial luminance of 5000 cd / m ² , room temperature, and DC constant current driving.

Comparative Example 2

In Example 8, the organic EL device was produced in the same manner as in Comparative Example 1 except that Compound H1 was used as the hole transporting material.

Table 1 shows the results of measuring the luminous efficiency of the obtained organic EL device, observing the luminous color, and measuring the half-life of light emission at initial luminance of 5000 cd / m ² , room temperature, and DC constant current driving.

As described in detail above, the aromatic amine derivative of the present invention reduces the driving voltage and is difficult to crystallize molecules, and the organic amine device is improved in yield by producing the organic EL device by containing it in the organic thin film layer. Long organic EL elements can be realized.

Claims (37)

An aromatic amine derivative represented by the following formula (1). [Formula 1]

In Formula 1, L ₁ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms, At least one of Ar ₁ to Ar ₄ is represented by the following formula (2), [Formula 2]

In Formula 2, R ₁ represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms , Substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted An alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group having 2 to 50 carbon atoms, a is an integer of 0 to 3, L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.} In Chemical Formula 1, each of Ar ₁ to Ar ₄ that is not Chemical Formula 2 independently represents a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, provided that a substituent of Ar ₁ to Ar ₄ is substituted or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms , Substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, halogen atom , Cyano group, nitro group, hydroxy group, or carboxyl group.] The method of claim 1, An aromatic amine derivative represented by Chemical Formula 2 is represented by the following Chemical Formula 3. [Formula 3]

{In Formula 3, R ₁ is a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.} The method according to claim 1 or 2, In Formula 1, Ar ₁ is an aromatic amine derivative represented by Formula 2. The method according to claim 1 or 2, Ar ₁ and Ar ₂ in the formula (1), each independently, an aromatic amine derivative represented by the formula (2). The method according to claim 1 or 2, Ar ₁ and Ar ₃ in the formula (1), each independently, an aromatic amine derivative represented by the formula (2). The method according to claim 1 or 2, In Formula 1, at least three of Ar ₁ to Ar ₄ are different from each other and are asymmetrical aromatic amine derivatives. The method according to claim 1 or 2, In Formula 1, three of Ar ₁ to Ar ₄ are the same and are asymmetrical aromatic amine derivatives. The method according to any one of claims 1 to 7, In Formula 1, Ar ₁ to Ar ₄ , each independently, represent a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group. The method according to any one of claims 1 to 8, In Formula 1, L ₁ is a biphenylene group, terphenylene group or fluorenylene group aromatic amine derivative. The method according to any one of claims 1 to 9, L 2 in the formula ₂ is phenyl group, a biphenyl group or a fluorene-ylene group aromatic amine derivative. The method according to any one of claims 1 to 10, In Formula 2, R ₁ is a phenyl group, naphthyl group or phenanthrene group aromatic amine derivative. The method according to any one of claims 1 to 11, In Formula 1, Ar ₁ to Ar ₄ are each independently a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group, L ₁ is a biphenylene group, a terphenylene group, or a fluorenylene group, and L in Formula 2 _An aromatic amine derivative which is a bivalent phenylene group, a biphenylene group, or a fluoreneylene group. Aromatic amine derivative represented by any one of the following formulas 4 to 6 [Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, L ₅ to L ₁₂ represent a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms, At least one of Ar ₅ to Ar ₉ is represented by the following formula (7), At least one of Ar ₁₀ to Ar ₁₅ is represented by the following formula (7), At least one of Ar ₁₆ to Ar ₂₁ is represented by the following formula (7), [Formula 7]

In Formula 7, R ₁ represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms , Substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, substituted or unsubstituted An alkoxycarbonyl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, or a carboxyl group having 2 to 50 carbon atoms, a is an integer of 0 to 3, L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.} In Formulas 4 to 6, Ar ₅ to Ar ₂₁ are each independently a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, provided that a substituent of Ar ₅ to Ar ₂₁ is substituted or unsubstituted An aryl group having 6 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, substituted or An unsubstituted aryloxy group having 5 to 50 nuclear atoms, a substituted or unsubstituted arylthio group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a halogen atom, a cyano Group, nitro group, hydroxyl group, or carboxyl group.] The method of claim 13, Aromatic amine derivatives represented by the following formula (8). [Formula 8]

{In Formula 8, R ₁ is a substituted or unsubstituted aryl group having 6 to 50 nuclear atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, L ₂ represents a substituted or unsubstituted arylene group having 6 to 50 nuclear atoms.} The method according to claim 13 or 14, At least one of Ar ₅ to Ar ₉ in Formula 4 is an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, In Formula 4, Ar ₅ is an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, Ar ₆ and Ar ₈ in Formula 4 are each independently an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, At least one of Ar ₁₀ to Ar ₁₅ in Formula 5 is an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, Ar ₁₀ and Ar ₁₅ in Formula 5 are each independently an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, Ar ₁₁ and Ar ₁₃ in Formula 5 are each independently an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, At least one of Ar ₁₆ to Ar ₂₁ in Formula 6 is an aromatic amine derivative represented by Formula 7. The method according to claim 13 or 14, Ar ₁₆ and Ar ₁₈ and Ar ₂₀ in Formula 6 are each independently an aromatic amine derivative represented by Formula 7. The method according to any one of claims 13 to 22, In Formulas 4, 5 and 6, Ar ₅ to Ar ₂₁ are each independently a phenyl group, a biphenyl group, a terphenyl group or a fluorenyl group. The method according to any one of claims 13 to 23, L ₅ to L ₁₂ in Chemical Formulas 4, 5, and 6 are each independently a phenylene group, a biphenylene group, a terphenylene group, or a fluorenylene group. The method according to any one of claims 13 to 24, An aromatic amine derivative wherein L ₂ in Formula 7 is a phenylene group, a biphenylene group, or a fluorenylene group. The method according to any one of claims 13 to 25, An aromatic amine derivative wherein R ₁ in Formula 7 is a phenyl group, a naphthyl group or a phenanthrene group. The method according to any one of claims 13 to 26, In Formulas 4, 5, 6, and 7, Ar ₅ to Ar ₂₁ are each independently a phenyl group, a biphenyl group, a terphenyl group, or a fluorenyl group, and L ₅ to L ₁₂ are each independently a phenylene group or a bi An aromatic amine derivative whose phenylene group, terphenylene group, or fluorenylene group, L <_2> is a phenylene group, a biphenylene group, or a fluoreneylene group. The method according to any one of claims 1 to 27, Aromatic amine derivative which is a material for organic electroluminescent elements. The method according to any one of claims 1 to 27, Aromatic amine derivative which is a hole transport material for organic electroluminescent elements. An organic electroluminescent device in which an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer is any one of claims 1 to 27. An organic electroluminescent device comprising the aromatic amine derivative described in the above alone or as a component of a mixture. The method of claim 30, An organic electroluminescent device in which the organic thin film layer has a hole transporting layer, and the aromatic amine derivative according to any one of claims 1 to 27 is contained in the hole transporting layer. The method of claim 30, An organic electroluminescent device in which the organic thin film layer has a plurality of hole transport layers, and the aromatic amine derivative according to any one of claims 1 to 27 is contained in a layer not directly in contact with the light emitting layer. The method of claim 30, An organic electroluminescence device in which the organic thin film layer has a hole injection layer, and the aromatic amine derivative according to any one of claims 1 to 27 is contained in the hole injection layer. The method of claim 30, An organic electroluminescent device in which the aromatic amine derivative according to any one of claims 1 to 27 is contained in the hole injection layer as a main component. The method according to any one of claims 30 to 34, wherein An organic electroluminescent device comprising a styrylamine compound and / or an arylamine compound in a light emitting layer. The method according to any one of claims 30 to 35, An organic electroluminescent element, wherein the layer in contact with the anode in the hole injection layer is a layer containing an acceptor material. The method according to any one of claims 30 to 36, An organic electroluminescent device emitting blue light.